Conversion of ethylene to butadiene



May 29, 1945 B. H. sHoEMAKER CONVERSION OF ETHYLENE TO BTADIENE Filed May 3Q, 1942 NMNSW 11 uw um, U

QNNNOPM 1 wwwa Patented May-29, i945 as'zaase coNvEasroN or mmm; ro Y nUrAnmNn Bernard B. Shoemaker, HammondMnd., assignor to Standard Oil Company, Chicago, Ill., a oorporation of Indiana museum my so, 1942, serai No. 445,110 s claims. (ci. zen-so) This invention relates to the manufacture of butadiene by a process of condensation from ethylene. The invention relates particularly to the manufacture of butadiene from ethylene in a According to my process an ethylene stream l' is divided and a part is subjected to a preliminary oxidation whereby oxidation products are produced which are subsequently .reacted with the other part of the ethylene stream in the presence of a catalyst having a dehydrating action, thereby eliminating oxygen from thel oxidized ethylene, principally as water, and effecting condensation between two molecules of ethylene. The initial oxidation of the ethylene is effected under controlled conditions in the presence of a catalyst selectedV to produce a substantial amount of ethylene oxide as a primary oxidation product. Acetaldehyde and other oxidation products may also be formed. 'I'he oxidation may be carried out with or without the addition of steam.

Referring to the drawing, ethylene or gases containing ethylene are charged to the process by line I leading to converter I I. Ethylene employed for this purpose may be found in the gases obtained from petroleum oil conversion processes, cracking, reforming. etc. Such gases `contain in addition to the ethylene appreciable amounts of ethane and small amounts of hydrogen, propane and propylene. These gases may contain from to 50% or more of ethylene by volume and may be charged to the process without separation, although it is desirable that the gases be free from hydrogen sulfide and sulfur compounds. The gases may also befractionated u'nder pressure to yield a C2 fraction containing a higher percentage of ethylene.

tion of silver nitrate followed by drying and gently igniting in the presence of a reducing` gas such as hydrogen. Another method involves the precipitation of silver oxalate on the support followed by ignition and reduction to metallic silver. The silver catalyst mayl be promoted with various other metals such as copper, gold, cobalt, nickel, iron, chromium, molybdenum, vanadium, and manganese. Antimony, bismuth and certain other elements may also be employed as catalysts. in converter II, but in'general the elements of Agroup IB of the periodic system are preferred.

It is important to control the temperature of the oxidation reaction in converter II within rather close limits, generally within the range'of about V150 to 400 C. For this purpose the converter is constructed with an extensive internal heat exchange surface indicated by tubes I2 in Converter II contains an oxidizing catalyst which is preferably silver deposited on a carrier. Suitable carriers are pumice, asbestos, silica gel, kieselguhr, acid treated clays, such as bentonite, montmorillonite, fullers earth, etc., bauxite, alumina and the like. A very eilective catalyst 'is made by impregnating silica ,gel with a soluthe cut-away portion. A cooling'or heating fluid is supplied to the exchanger tubes by connections I3 and I4. A suitable fluid for the purpose is water -under pressure, oil, molten salts, or molten metal or alloy, e. g., lead or a lead bismuth alloy. The -pressure employed in converter II may vary overwide limits from atmospheric to '700 pounds per square inch, although generally pressures of 50 to 400 pounds per square inch are preferred.

Oxygen required for the oxidation reaction in l converter II is supplied by line I5 connected to a source -of oxygen or air or other oxygen-con'- taining gas. The amount of oxygen supplied is carefully controlled, usually within the range of about 0.0 5 to 5 mols of oxygen per mol of ethylene treated. An oxygen mol ratio of about 0.2 to 1 is generally satisfactory. Water or steam may also be supplied to the converted by line I6, either mixed with the ethylene feed gases as indicated or charged to the converter `at a plurality of points in the path of the gases flowing. therethrough. The introduction of water in this way may be employed to assist in controlling the tem perature and absorbing the heat evolved in the reaction. Water in'the reaction also tends to increase the production of ethylene oxide and reconverter II.

ldrating, type. Suitable catalysts are aluminum loxide, thorium oxide, magnesium oxide, zinc oxide, alumina deposited on silica gel, alumina gel and bauxite or mixtures of any of them. 1 Small amounts of oxides of vanadium, chromium or i molybdenum maybe present as promoters. Alumina gel prepared from the gelatin of alumina sols is particularly effective.

r Instead of adding additional ethylene to the ethylene oxidation products charged to reactor I8,

I prefer to `employ an excess of ethylene in the initial oxygen-ethylene mixture charged to conin the oxidation products transferred to the second step of the process for that reaction.

, The temperature of the reaction in I8 may be 1 within the range of about 350 to 650l C., prefl erably about 400 to 500? C. The reaction 'may be verter II, sufilcient ethylene remaining unreacted conducted at atmospheric pressure, although suresof the order of 4 to 10- atmospheres abso- .l lute may -be employed. The amount of ethylene employed is vpreferably about l to 4 mols per mol of oxygen in the oxidationproducts from The ethylene stream may be heat- 3 ed in heater 20 to a temperature above the reaci tion temperature suiiicient to provide heat for the reaction in I8. 'I'he time of contact in the reactor I8 is about 1 to 50 seconds, when operating at` g about atmospheric pressure, preferably about 5 to I 20 seconds, depending on temperature, catalyst activity, etc. When operating at higher pressure,

relatively longer contact time, e. g., 40 to 100 1 seconds, is employed. Feed rates ofthe order of Q 1/2 to 10 kilograms of charge per liter of catalyst #are satisfactory.

The gaseous products from I8 are cooled rapidcondenser 2B and receiver 21. The temperature of condenser 26 should be maintained well below l the boiling point of butadiene, i. el, below about `4" C. Refrigeration will be required. a suitable refrigerant being'liquid ammonia capable of producinga temperature of `40 C. when desired. l Vapor line 28 may be employed' to conduct away from-the receiver gaseous products uncondensed Where the amount of such case where air is supplied to the process at I5,

by line 29 and may be further rei-ined by fractionation or extraction to remove oxygen 'compounds, etc.

From the bottom of fractionator 2l there may` reduced pressures or superatmospheric presi ly below the temperature of further reaction after l removing from the reactor I8 and this may be most easily accomplished by introducing a quenching liquid at 2 I A tubular cooler or condenser 22 may also be employed. A suitable l quenching liquid may be water or a quenching oil. Means are provided for the subsequent separation f of the water or oil from valuable reaction products. From cooler 22 the reaction products are conducted by line 23 to fractionator 2l wherein the vapors of butadiene are withdrawn by line 25 to be eliminated by line III a heavy product fraction, including the quenching oil or water supplied at 2| when used. Water produced in the reaction will also be eliminated at this point. In converter II and also in reactor I8, the catalyst may be regenerated by burning with air or oxygen to remove carbonaceous deposits, care being taken to control the temperature and prevent damage to the catalyst by overheating, Regeneration temperatures of 500 to 650 C. are usually suitable.

The life of the catalyst in I8 may also be increased and fthe concentration of butadiene in the iinal product may be increased by subjecting the oxidation' products from II to a preliminary fractionation before charging to the reactor I8. This may be done by diverting the stream in line I1 through fractionator 38 by closing 'valve 85 and opening valves 38 and 31. In fractionator. 84 there is eliminated any heavy products, for example, water and other products boiling above 30 C. at atmospheric pressure, line 88 being provided forthis purpose. Reux coil 39 effects the condensation of ethylene oxide, acetaldehyde, or other low boiling products, allowing nitrogen, C02, CO, etc.,to be discharged from the system by liney 4I. 'I'he ethylene oxide, aldehyde and other light oxidation products forming a fraction boiling below about 30 C. are withdrawn by valve 31 and line Il and are charged by line I1 to reactor I8 as hereinbefore described. When operating reactor I8 with the fractionated oxidation products in this manner, the recoveryof butadiene from the process is considerably simplied. The reactions involved in my process are not thoroughly understood but it is believed that one of the important reactions is the formation of ethylene oxide in the oxidation stage followed by the condensation of ethyleneV oxide and ethylene in the condensation stage. The condensation reaction may proceed through the formation of an intermediate product which may be tetrahydrofurane, or butadiene may be formed directly from the ethylene oxide` and ethylene without the formation ofy an intermediate compound. Intermediate compounds which may be formed, such as tetrahydrofurane, which are not immediately converted in the dehydration step to butadiene, may be recovered from the process and recycled to the dehydration step. Such substances boiling above the boiling point of butadiene may be recovered by refractionating the heavier fraction withdrawn by line 80.

' Instead of employing the catalysts in iixed beds asl shown in the drawing, I may employ moving catalyst beds to which fresh catalyst is continuously or periodically added and from which spent catalyst is withdrawn for discard or regeneration. I may also operate with upilowing vapors and suspended catalyst which may be in the form of nne granules or powder. When employing suspended catalyst in the oxidation step,- I may continuouslywithdraw, cool and return catalyst to the reactor as a means of controlling the temperature therein. 1'

Although I have described my process with re- I 2,376,936 oxygen per moi of ethylene treated, and thereafter condensing additional ethylene with said oxidation products in a second stage of the process in the presence of a dehydrating catalyst.

2. The process of claim l vwherein the oxidation of ethylene is conducted in the presence of a silver catalyst.

3. The process of claim 1 wherein the said dehydrating catalyst is aluminum oxide.

4. The process of claim 1 wherein the condensation of ethylene and oxidized ethylene is effected in the presence of aluminum oxide at a temperature within the range of 350 to 650 C.

5. The process of making butadiene which comprises oxidizing ethylene with oxygen in the pro- I portion of .05 to 5 mois per mol of ethylene in the presence of a silver catalyst at a temperaturewithin the range of about 150 to 400 C., recovering by fractionation from the oxidation products a liquid boiling below about 30 C., contacting said fraction and ethylene for a period oi about 1 to 50 seconds, with a. dehydrating catalyst main'- tained at a-temperature within the range oi' about 350 to 650 C., rapidly cooling the products "of 'said reaction, separating butadiene and ethylene from said products and returning said ethylene to sam aehydraung catalyst.

6. The process of claim 5 wherein the dehydrating catalyst is aluminum oxide.

7. The process ot making butadiene which coniprises subjecting a mixture of ungen and ethylen e. in the ratio oi' about .05 to 5 mois of oxygen per mol of ethylene. to the action of an oxidizing catalyst under controlled temperature conditions,

vbetween about 150 and 400 C., whereby oxidation products oi' ethylene are produced, passing the resulting oxidation products and excess ethylene into contact with a dehydrating catalyst maintained at a temperature above that employed in -said oxidation reaction, thereby eilecting dehy- BERNARD H. SHOEMAKER. 

